U.S. patent application number 12/406571 was filed with the patent office on 2009-09-24 for methods of making cyclododecatriene and methods of making laurolactone.
This patent application is currently assigned to INVISTA NORTH AMERICA S.A.R.L.. Invention is credited to GURUSAMY RAJENDRAN.
Application Number | 20090240068 12/406571 |
Document ID | / |
Family ID | 41089582 |
Filed Date | 2009-09-24 |
United States Patent
Application |
20090240068 |
Kind Code |
A1 |
RAJENDRAN; GURUSAMY |
September 24, 2009 |
METHODS OF MAKING CYCLODODECATRIENE AND METHODS OF MAKING
LAUROLACTONE
Abstract
The present disclosure provides processes for the preparation of
dodecanedioic acid (DDDA).
Inventors: |
RAJENDRAN; GURUSAMY; (League
City, TX) |
Correspondence
Address: |
INVISTA NORTH AMERICA S.A.R.L.
THREE LITTLE FALLS CENTRE/1052, 2801 CENTERVILLE ROAD
WILMINGTON
DE
19808
US
|
Assignee: |
INVISTA NORTH AMERICA
S.A.R.L.
Wilmington
DE
|
Family ID: |
41089582 |
Appl. No.: |
12/406571 |
Filed: |
March 18, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61037861 |
Mar 19, 2008 |
|
|
|
Current U.S.
Class: |
549/272 ;
562/537 |
Current CPC
Class: |
C07C 51/316 20130101;
C07D 313/00 20130101; C07C 29/172 20130101; C07C 45/53 20130101;
C07C 2601/20 20170501; C07C 29/172 20130101; C07C 35/205 20130101;
C07C 45/53 20130101; C07C 49/413 20130101; C07C 51/316 20130101;
C07C 53/126 20130101 |
Class at
Publication: |
549/272 ;
562/537 |
International
Class: |
C07C 51/31 20060101
C07C051/31; C07D 313/00 20060101 C07D313/00 |
Claims
1. A process for making dodecanedioic acid comprising: contacting
1,3-butadiene with a first catalyst and forming
cyclododeca-1,5,9-triene; oxidizing the cyclododeca-1,5,9-triene
using an oxygen containing reagent to form
epoxycyclododeca-5,9-diene, converting the
epoxycyclododeca-5,9-diene into a first mixture comprising
cyclododecanol and cyclododecanone; and contacting the first
mixture with reactants comprising a third catalyst and nitric acid
to form a second mixture comprising dodecanedioic acid.
2. The method of claim 1, wherein the first catalyst is a
homogeneous Ziegler-Natta type catalyst.
3. The method of claim 1, wherein the step of oxidizing the
cyclododeca-1,5,9-triene is conducted in the presence of a second
catalyst.
4. The method of claim 1, wherein the second catalyst is selected
from: hydrocarbon soluble Mo naphthenate, hydrocarbon soluble V
naphthenate, hydrocarbon soluble Ti naphthenate, and a combination
thereof.
5. The method of claim 1, wherein the step of converting the
epoxycyclododeca-5,9-diene into a first mixture includes converting
the epoxycyclododeca-5,9-diene into the first mixture using a
process selected from a selective reduction, rearrangement, or a
combination thereof.
6. The method of claim 1, wherein the third catalyst is selected
from: ammonium meta-vanadate and copper nitrate.
7. The method of claim 1, wherein cyclododecanol is about 30% to
70% of the first mixture, and wherein the cyclododecanone is about
70% to 30% of the first mixture.
8. The method of claim 1, wherein the dodecanedioic acid is about
40% to 90% of the second mixture.
9. The method of claim 1, wherein the oxygen containing reagent is
a mixture that includes oxygen.
10. The method of claim 1, wherein the oxygen containing reagent is
a mixture selected from the group consisting of: air enriched with
pure oxygen, pure oxygen and pure nitrogen, and a combination
thereof.
11. The method of claim 10, wherein the mixture includes an amount
of oxygen to provide oxygen to the reaction in an amount of about
1% to 99%.
12. The method of claim 1, wherein the step of oxidizing the
cyclododeca-1,5,9-triene using an oxygen containing reagent further
comprises an initiator selected from the group consisting of: AlBN,
organic peroxides and, an azo-initiator.
13. The method of claim 1, wherein the step of oxidizing the
cyclododeca-1,5,9-triene using an oxygen containing reagent is
conducted at a reaction temperature of about 50.degree. C. to
220.degree. C. and at a pressure of about 50 psig to 500 psig.
14. The method of claim 1, wherein the step of oxidizing the
cyclododeca-1,5,9-triene using an oxygen containing reagent further
comprising a metal catalyst.
15. The method of claim 1, wherein the step of oxidizing the
cyclododeca-1,5,9-triene using an oxygen containing reagent is
carried out continuously using a fixed bed catalyst.
16. A process for making laurolactone comprising: providing a
reaction vessel including a solution of cyclododecanone (CDDK) that
is dissolved in a about an equal weight of an acid anhydride;
providing to the vessel an acid catalyst in an amount effective to
promote the reaction, wherein the acid catalyst is selected on the
basis of its pK.sub.a such that its pK.sub.a is about 0 to about 5;
and introducing hydrogen peroxide to the reaction vessel to promote
the Baeyer-Villiger oxidation, wherein about 20% or more of the
cyclododecanone (CDDK) is converted to laurolactone.
17. The method of claim 16, wherein the acid catalyst is selected
from the group consisting of: dichloroacetic acid and a
peracid.
18. The method of claim 16, wherein the hydrogen peroxide is in an
amount of about 1 to 10 moles hydrogen peroxide per mole of CDDK
present in the mixture.
19. The method of claim 16, wherein amount effective to promote the
reaction is in an amount of about 1 to 10 moles acid catalyst per
mole of CDDK present in the mixture.
20. A process for making dodecanedioic acid comprising: contacting
1,3-butadiene with a first catalyst and forming
cyclododeca-1,5,9-triene; oxidizing the cyclododeca-1,5,9-triene
using an oxygen containing reagent to form
epoxycyclododeca-5,9-diene, converting the
epoxycyclododeca-5,9-diene into a first mixture comprising
cyclododecanol and cyclododecanone; disposing the cyclododecanone
(CDDK) from the first mixture in a reaction vessel, wherein the
CDDK is dissolved in a about an equal weight of an acid anhydride;
providing to the vessel an acid catalyst in an amount effective to
promote the reaction, wherein the acid catalyst is selected on the
basis of its pK.sub.a such that its pK.sub.a is about 0 to about 5;
and introducing hydrogen peroxide to the reaction vessel to promote
the Baeyer-Villiger oxidation, wherein about 20% or more of the
(CDDK) is converted to laurolactone.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. provisional
application entitled, "CYCLODODECATRIENE AND CHEMICAL PROCESS",
having Ser. No. 61/037,861, filed on Mar. 19, 2008, which is
entirely incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The disclosure herein relates to a process for forming a
mixture containing dodecanedioic acid (DDDA).
BACKGROUND
[0003] It is known to produce dodecanedioic acid (DDDA) using a
chemical process starting with the conversion of 1,3-butadiene
(trimerization) to 1,5,9-cyclododecatriene (CDDT). This
trimerization process employs a Ziegler-Natta catalyst (TiCl.sub.4
and aluminum chloride) and mild 70 to 80.degree. C. conditions at
ca. 2 bar pressure absolute. Followed by reduction of the CDDT to
cyclododecane using hydrogen and Raney Nickel catalyst at 170 to
180.degree. C. and 26-28 bar pressure absolute, the cyclododecane
is oxidized with air to a mixture comprising cyclododecanol (CDDA)
and cyclododecanone (CDDK) in the presence of a boric acid catalyst
at 160 to 180.degree. C. and 1-2 bar pressure absolute. The CDDK
and CDDA mixture contains about 80-90% CDDA and 10-20% CDDK. This
mixture is oxidized using nitric acid and catalysts comprising
copper and vanadium to obtain a mixture comprising DDDA.
SUMMARY
[0004] Briefly described, embodiments of this disclosure include
processes of making dodecanedioic acid (DDDA), and the like. One
exemplary process for making dodecanedioic acid, among others,
includes: contacting 1,3-butadiene with a first catalyst and
forming cyclododeca-1,5,9-triene; oxidizing the
cyclododeca-1,5,9-triene using an oxygen containing reagent to form
epoxycyclododeca-5,9-diene, converting the
epoxycyclododeca-5,9-diene into a first mixture comprising
cyclododecanol and cyclododecanone; and contacting the first
mixture with reactants comprising a third catalyst and nitric acid
to form a second mixture comprising dodecanedioic acid.
[0005] One exemplary process for making laurolactone, among others,
includes: providing a reaction vessel including a solution of
cyclododecanone (CDDK) that is dissolved in about an equal weight
of an acid anhydride; providing to the vessel an acid catalyst in
an amount effective to promote the reaction, wherein the acid
catalyst is selected on the basis of its pK.sub.a such that its
pK.sub.a is about 0 to about 5; and introducing hydrogen peroxide
to the reaction vessel to promote the Baeyer-Villiger oxidation,
wherein about 20% or more of the cyclododecanone (CDDK) is
converted to laurolactone.
[0006] One exemplary process for making laurolactone, among others,
includes: contacting 1,3-butadiene with a first catalyst and
forming cyclododeca-1,5,9-triene; oxidizing the
cyclododeca-1,5,9-triene using an oxygen containing reagent to form
epoxycyclododeca-5,9-diene, converting the
epoxycyclododeca-5,9-diene into a first mixture comprising
cyclododecanol and cyclododecanone; disposing the cyclododecanone
(CDDK) from the first mixture in a reaction vessel, wherein the
CDDK is dissolved in about an equal weight of an acid anhydride;
providing to the vessel an acid catalyst in an amount effective to
promote the reaction, wherein the acid catalyst is selected on the
basis of its pK.sub.a such that its pK.sub.a is about 0 to about 5;
and introducing hydrogen peroxide to the reaction vessel to promote
the Baeyer-Villiger oxidation, wherein about 20% or more of the
(CDDK) is converted to laurolactone.
DETAILED DESCRIPTION
[0007] Before the present disclosure is described in greater
detail, it is to be understood that this disclosure is not limited
to particular embodiments described, as such may, of course, vary.
It is also to be understood that the terminology used herein is for
the purpose of describing particular embodiments only, and is not
intended to be limiting, since the scope of the present disclosure
will be limited only by the appended claims.
[0008] Unless defined otherwise, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which this disclosure belongs.
Although any methods and materials similar or equivalent to those
described herein can also be used in the practice or testing of the
present disclosure, the preferred methods and materials are now
described.
[0009] All publications and patents cited in this specification are
herein incorporated by reference as if each individual publication
or patent were specifically and individually indicated to be
incorporated by reference and are incorporated herein by reference
to disclose and describe the methods and/or materials in connection
with which the publications are cited. The citation of any
publication is for its disclosure prior to the filing date and
should not be construed as an admission that the present disclosure
is not entitled to antedate such publication by virtue of prior
disclosure. Further, the dates of publication provided could be
different from the actual publication dates that may need to be
independently confirmed.
[0010] Embodiments of the present disclosure will employ, unless
otherwise indicated, techniques of chemistry, chemical engineering,
and the like, which are within the skill of the art. Such
techniques are explained fully in the literature.
[0011] It must be noted that, as used in the specification and the
appended claims, the singular forms "a", "an", and "the" include
plural referents unless the context clearly dictates otherwise.
Thus, for example, reference to "a support" includes a plurality of
supports. In this specification and in the claims that follow,
reference will be made to a number of terms that shall be defined
to have the following meanings unless a contrary intention is
apparent.
Discussion
[0012] Embodiments of the present disclosure provide for a process
for making dodecanedioic acid (DDDA). Embodiments of the present
disclosure may have certain advantages in energy consumption versus
other methods. In general, embodiments of the present disclosure
require less energy in the conversion of cyclododeca-1,5,9-triene
to cyclododecanol (CDDA) or cyclododecanone (CDDK) in comparison to
a process disclosed by Welton in his U.S. Pat. No. 3,607,948
(assigned to E. I. du Pont de Nemours and Co.); the disclosure of
Welton are herein incorporated by reference in their entirety.
[0013] In general, embodiments of this disclosure relate to
processes for the preparation of dodecanedioic acid (DDDA) by
oxidizing cyclododeca-1,5,9-triene with an oxygen containing
reagent to form epoxycyclododeca-5,9-diene, forming a mixture
containing cyclododecanol and cyclododecanone, and oxidizing the
mixture with nitric acid to form a DDDA containing mixture of
diacids.
[0014] Embodiments of this disclosure relate to processes of
chemical transformation employing the steps of polymerizing
(trimerization) of 1,3-butadiene to cyclododeca-1,5,9-triene, which
is subsequently oxidized to form epoxycyclododeca-5,9-diene. Then,
epoxycyclododeca-5,9-diene is converted by selective reduction
and/or rearrangement to a first mixture containing cyclododecanol
(CDDA) and cyclododecanone (CDDK). Next, the first mixture is
oxidized to a second mixture comprising dodecanedioic acid (DDDA).
Reduction of the cyclododeca-1,5,9-triene (CDDT) to cyclododecane
with hydrogen over a heterogeneous Raney Nickel catalyst is not
performed in this process and no catalyst is employed in the
intermediate steps of this transformation as compared with the
known method of employing air oxidation in the presence of boric
acid. Ways to perform the oxidation of cyclododeca-1,5,9-triene to
the epoxycyclododeca-5,9-diene are known from T. Sridhar et al.
(Department of Chemical Engineering, Monash University, Victoria
3800, Australia) found in Ind. Eng. Chem. Res., 46 (10), 3057-3062,
2007 "Uncatalyzed Oxidation of 1,5,9-Cyclododecatriene with
Molecular Oxygen."
[0015] In an embodiment, the process includes contacting
3-butadiene (BD) with a first Ziegler-Natta type catalyst effective
for trimerizing BD and forming cyclododeca-1,5,9-triene (CDDT).
Next, the process includes oxidizing the cyclododeca-1,5,9-triene
(CDDT), using an oxygen containing reagent, to form
epoxycyclododeca-5,9-diene (ECDDD). In an embodiment, the
oxidization can be conducted in the presence of a second catalyst.
Subsequently, the process includes converting
epoxycyclododeca-5,9-diene (ECDDD) into a first mixture comprising
cyclododecanol (CDDA) (e.g., about 30% to 70% of the first mixture)
and cyclododecanone (CDDK) (e.g., about 70% to 30% of the first
mixture). The conversion can be conducted using selective reduction
and/or rearrangement. Next, the process includes contacting the
first mixture with a third catalyst (e.g., ammonium meta-vanadate
and copper nitrate) and nitric acid, which results in forming a
second mixture comprising dodecanedioic acid (DDDA) (e.g., about
40% to 90% of the second mixture).
[0016] In an embodiment, a process for making dodecanedioic acid
can include contacting 1,3-butadiene with a first catalyst
effective for trimerization and forming cyclododeca-1,5,9-triene
(CDDT) and minor amounts of 1,3-butadiene dimers, i.e.,
cylcooctadiene and vinyl cyclohexene.
##STR00001##
[0017] In an embodiment, the first catalyst (also referred to as a
"trimerization catalyst") may be a homogeneous Ziegler-Natta type;
e.g., TiCl.sub.4 and aqueous aluminum chloride (AlCl), or
diethyl-AlCl.
[0018] Next, the process includes oxidizing the
cyclododeca-1,5,9-triene using an oxygen containing reagent to form
epoxycyclododeca-5,9-diene. In an embodiment, a second catalyst
(e.g., hydrocarbon soluble Mo, V, or Ti naphthenates) can be used
to form epoxycyclododeca-5,9-diene. However, in an embodiment, a
second catalyst is not required to form
epoxycyclododeca-5,9-diene.
##STR00002##
[0019] Subsequently, the process includes converting the
epoxycyclododeca-5,9-diene into a first mixture comprising
cyclododecanol and cyclododecanone. In an embodiment, the
conversion can be performed by selective reduction and
rearrangement such as those listed here:
##STR00003##
[0020] Next, the process includes contacting the first mixture with
a third catalyst (ammonium meta-vanadate and copper nitrate) and
nitric acid (e.g., concentrated nitric acid), which forms
dodecanedioic acid (and minor amounts of linear dicarboxylic acids
including those of fewer than 12 carbon atoms).
[0021] This mixture (second mixture) resulting from the nitric
oxidation contains the C.sub.11 dicarboxylic acid (e.g., about 1%
to 5% of the second mixture), as well as, smaller amounts of the
C.sub.6 to C.sub.10 dicarboxylic acids (e.g., about 1% to 5% of the
second mixture).
##STR00004##
[0022] In an embodiment, the oxidation process of
cyclododeca-1,5,9-triene to epoxycyclododeca-5,9-diene and other
mono-oxygen substituted cyclododecatrienes (e.g., alcohol and
ketone substituents), herein disclosed, may be achieved by
semi-continuous and continuous processes in the presence of oxygen
gas. In an embodiment, the oxygen gas is about 1 and 99.5% of the
gas, with the remaining balance being nitrogen gas. In an
embodiment, the product yields can be about 60 and 96%, while
conversion to product is about 10 and 99%.
[0023] In an embodiment, the process for oxidation of
cyclododeca-1,5,9-triene to epoxycyclododeca-5,9-diene and other
mono-oxygen substituted cyclododecatrienes, herein disclosed, is
achievable in semi-continuous and continuous processes in the
presence of oxygen gas. In an embodiment, the oxygen gas is about 1
and 99.5%, and the remaining balance being a synergistic gas such
as carbon dioxide or an inert gas such as argon. It should be noted
that synergistic gases can enhance the solubility of oxygen at
temperatures and pressures where nitrogen provides no such synergy
in enhancing solubility of the oxygen. In an embodiment, the
enhanced solubility of oxygen in cyclododeca-1,5,9-triene results
in higher conversion and selectivity to product. In an embodiment,
the product yields achievable are about 80 and 96%, while the
conversion to product is about 40 and 99%.
[0024] In an embodiment, the process provided herein for preparing
epoxycyclododeca-5,9-diene and other mono-oxygen substituted
cyclododecatrienes is achievable by reacting
cyclododeca-1,5,9-triene with 99.9% pure oxygen at temperatures of
about 50.degree. C. to 150.degree. C. and at pressures of about 50
psig to 250 psig.
[0025] In an embodiment, the process provided herein for preparing
epoxycyclododeca-5,9-diene along with other mono-oxygen substituted
cyclododecatrienes by reacting cyclododeca-1,5,9-triene with air at
temperatures of about 60.degree. C. to 220.degree. C. and at
pressures of about 60 psig to 500 psig.
[0026] In an embodiment, the process provided herein for preparing
epoxycyclododeca-5,9-diene along with other mono-oxygen substituted
cyclododecatrienes is achievable by reacting
cyclododeca-1,5,9-triene with a mixture of air and pure oxygen or
nitrogen. In an embodiment, the mixture includes air enriched with
pure oxygen or pure oxygen and pure nitrogen providing the balance
of the composition. In an embodiment, the combination of air and
pure oxygen comprise a composition providing oxygen to the reaction
in an amount from about 1% to about 99%. Similarly, the combination
of pure nitrogen and pure oxygen may comprise a composition
providing oxygen to the reaction in an amount from about 1% to
about 99%. In an embodiment, the reaction temperature for this
process can be about 50.degree. C. to 220.degree. C. at pressures
of about 50 psig to 500 psig.
[0027] In an embodiment, the process provided herein for preparing
epoxycyclododeca-5,9-diene along with other mono-oxygen substituted
cyclododecatrienes is achievable, in a continuous process, by
reacting cyclododeca-1,5,9-triene with a mixture of air and pure
oxygen or pure oxygen and nitrogen. In an embodiment, the mixture
includes air enriched with pure oxygen or pure oxygen and pure
nitrogen providing the balance of the composition. In an
embodiment, the combination of air and pure oxygen comprise a
composition providing oxygen to the reaction in an amount from
about 1% to about 99%. Similarly, the combination of pure nitrogen
and pure oxygen may comprise a composition providing oxygen to the
reaction in an amount from about 1% to about 99%. In an embodiment,
this step can be conducted in the presence of initiators chosen
from among AlBN, organic peroxides (e.g., t-butyl hydroperoxide),
or other azo-initiators (e.g., t-butyl carbonyl azide). However,
the presence of the initiators is not required.
[0028] In an embodiment, the process provided herein for preparing
epoxycyclododeca-5,9-diene along with other mono-oxygen substituted
cyclododecatrienes is achievable by reacting
cyclododeca-1,5,9-triene with a mixture of air and pure oxygen or
pure oxygen and nitrogen. In an embodiment, the mixture includes
air enriched with pure oxygen or pure oxygen and pure nitrogen
providing the balance of the composition. In an embodiment, the
combination of air and pure oxygen comprise a composition providing
oxygen to the reaction in an amount from about 1% to about 99%.
Similarly, the combination of pure nitrogen and pure oxygen may
comprise a composition providing oxygen to the reaction in an
amount from about 1% to about 99%. In an embodiment, this step can
be conducted with the aid of a metal catalyst such as silver,
nickel, iron and/or cobalt. In an embodiment, this step is not
conducted with a metal catalyst.
[0029] In an embodiment, the process provided herein for preparing
epoxycyclododeca-5,9-diene and other mono-oxygen substituted
cyclododecatrienes is achievable by reacting
cyclododeca-1,5,9-triene (CDDT) with a mixture of air and pure
oxygen or pure oxygen and nitrogen. In an embodiment, the mixture
includes air enriched with pure oxygen or pure oxygen and pure
nitrogen providing the balance of the composition. In an
embodiment, the combination of air and pure oxygen comprise a
composition providing oxygen to the reaction in an amount from
about 1% to about 99%. Similarly, the combination of pure nitrogen
and pure oxygen may comprise a composition providing oxygen to the
reaction in an amount from about 1% to about 99%. In an embodiment,
the reaction can be carried out continuously using a fixed bed
catalyst chosen from among of the metals: silver, nickel, iron
and/or cobalt (the active metal supported on a catalyst support can
include aluminum oxide, silicon dioxide or activated carbon).
[0030] In an embodiment, this continuous process can be
advantageously carried out at with varying CDDT feed rates. Useful
feed rates for CDDT are about 1 liter per hour to 5 liters per hour
in a continuously circulating process stream. In an embodiment, the
residence time is advantageously varied from about 2 minutes to 150
minutes and for times of about 10 minutes to 120 minutes. In an
embodiment, the reaction temperature can advantageously be about
50.degree. C. to 200.degree. C., and the temperature can be about
80.degree. C. to 160.degree. C. The yields of
epoxycyclododeca-5,9-diene and other mono-oxygen substituted
cyclododecatrienes can be about 60 to 99% with a conversion. of the
starting material cyclododeca-1,5,9-triene to products of about 10
to 99%.
[0031] The process provided herein for preparing cyclododecanol
(CDDA) is achievable using noble metal catalysts (Pd, or Pt
supported on appropriate supports including, but not limited to,
aluminum oxide, silicon dioxide and activated carbon) at hydrogen
gas pressures of about 500 psig to 4500 psig. Starting with
epoxycyclododeca-5,9-diene along with mono-oxygen substituted
cyclododecatrienes a substantially complete hydrogenation to
cyclododecanol (CDDA) is achievable. In an embodiment, the CDDA
yields in the process can be about 96% to 99.9% with a conversion
to product about 95% to 99%.
[0032] In an embodiment of the present disclosure, a mixture of
cyclododecanone (CDDK), which may be obtained from an embodiment of
the present disclosure described above, can be used to make
laurolactone. In an embodiment, the process includes providing to a
reaction vessel including a solution of cyclododecanone (CDDK) that
is dissolved in a substantially equal weight of an acid anhydride
(e.g., acetic anhydride, maleic anhydride, or the like) and
providing to the vessel an acid catalyst. In an embodiment, the
acid catalyst can be provided in an amount effective to promote the
reaction, e.g., 0.5% to 10% by weight based on the amount of CDDK
present. In an embodiment, the acid catalyst can be selected on the
basis of its pK.sub.a such that its pK.sub.a is about 0 to about 5
(e.g., dichloroacetic acid or a peracid such as trifluoroperacetic
acid, and the like). In addition, the process includes introducing
hydrogen peroxide (e.g., 1 to 10 moles hydrogen peroxide per mole
of CDDK present or a similar amount of peracid such as
trifluoroperacetic acid, for example) to the vessel and promoting
the Baeyer-Villiger oxidation of cyclododecanone (CDDK) and
converting a substantial portion (e.g., about 20% or more of the
CDDK is converted) of the cyclododecanone (CDDK) to
laurolactone.
Test and Analytical Methods
[0033] In general, oxidation of cyclododeca-1,5,9-triene in
foregoing process scheme may be monitored by the rate of uptake of
oxygen, as well as, by taking samples intermittently during the
reaction. It is convenient, as one skilled in the art would know,
to analyze the samples taken intermittently or in the case of final
reaction products by chromatographic methods, e.g., GC, GC-MS, HPLC
and by spectroscopic methods, e.g., .sup.1H NMR and .sup.13C NMR,
and also infrared (IR) methods.
[0034] All gas chromatographic (GC) analysis may be performed using
an AGILENT TECHNOLOGIES 6890 equipped with AGILENT DB-FFAP column
(25 m.times.0.20 mm.times.0.3 .mu.m) with injector and detector
temperatures kept at 250.degree. C. Such samples are conveniently
analyzed using hexadecane as an internal standard at 120.degree. C.
isothermal with helium as a carrier gas.
[0035] Gas chromatography mass spectrometry (GC-MS) analysis is
performed on an AGILENT TECHNOLOGIES 6890 with a Model 5973-MSD
(mass-selective detector) equipped with an Agilent DB-FFAP column
(25m.times.0.20 mm.times.0.3 .mu.m). The injector and detector
temperatures are maintained at 250.degree. C. The samples are
analyzed using hexadecane as the internal standard at 120.degree.
C. isothermal with helium as the carrier gas.
[0036] Proton (.sup.1H) NMR and Carbon (.sup.13C) NMR is done using
a Varian 500 MHz NMR equipped with tuning probe. Selective
decoupling and homo- and hetero-nuclear NOE experiments may be
performed to establish the geometry and positions of oxygen groups
in the product.
[0037] Pressures reported herein refer to pounds per square inch
gauge (psig) which include the pressure of one atmosphere (14.7
pounds per square inch).
[0038] Absolute pressures in kilopascals (kPa) are referenced from
vacuum. One pound per square inch is about 6.9 kPa.
EXAMPLES
[0039] Now having described the embodiments of the present
disclosure, in general, the following Examples describe some
additional embodiments of the present disclosure. While embodiments
of the present disclosure are described in connection with the
following examples and the corresponding text and figures, there is
no intent to limit embodiments of the present disclosure to this
description. On the contrary, the intent is to cover all
alternatives, modifications, and equivalents included within the
spirit and scope of embodiments of the present disclosure.
Example 1
[0040] In an example, cyclododeca-1,5,9-triene (40.5 grams, 0.25
mole) is introduced to an autoclave reactor along with a suitable
initiator (0.35% w/w). The autoclave is sealed and the internal air
is displaced by introducing nitrogen gas. The autoclave is provided
with agitation and heating to 100.degree. C. After the autoclave
reactor temperature is attained (100.degree. C.) the nitrogen gas
is displaced with pure oxygen gas at a pressure of 80 pounds per
square inch gage (psig), ca. 450 kPa absolute. The reaction is run
in a semi-continuous mode. The pressure in the reactor is
maintained continuously with the aid of a control valve set at 80
psig while the outlet valve from the reactor is closed. The
reaction temperature is controlled at 100.+-.3.degree. C. with the
aid of a cooling loop inside the reactor. Samples are taken
intermittently to monitor the progress of the reaction. Each sample
is quantitatively analyzed by the analytical methods disclosed
above. The reaction is stopped at the end of 2.5 hours, cooled to
below 30.degree. C. and vented to ambient pressure. The contents
are transferred to glass vessel for peroxide decomposition and
product isolation. The selectivity of this reaction to
epoxycyclododeca-6-10-diene and other mono-oxygenated products like
alcohol (CDDA) and ketone (CDDK) is 96%. The conversion of
cyclododeca-1,5,9-triene to the epoxide (ECDDD) and mono-oxygenated
products is 88%.
Example 2
[0041] In another example; cyclododeca-1,5,9-triene (40.5 grams,
0.25 mole) is charged into an autoclave reactor along with an
initiator (0.35% w/w); as in Example 1. The autoclave is sealed and
the air displaced by nitrogen. Agitation is started and the
autoclave heated to 110.degree. C. After the reactor temperature
attain, the 110.degree. C. nitrogen gas is flushed with pure oxygen
and pressurized to 100 psig; ca. 790 kPa. The reaction is run in a
semi-continuous mode. The pressure in the reactor is maintained
continuously with the aid of a control valve set at 110 psig, while
an outlet valve from the reactor is closed. The reaction
temperature may be controlled at 110.+-.3.degree. C. with the aid
of a cooling loop inside the reactor. Samples are taken
intermittently and quantitatively analyzed by the foregoing
analytical methods to monitor the progress of the reaction. The
reaction is stopped at the end of 2 hours, cooled to <30.degree.
C. and vented to ambient pressure. The contents may be transferred
to glass vessel for the peroxide decomposition and product
isolation. The selectivity of this reaction to epoxy
cyclododeca-6-10-diene and other mono-oxygenated products like
alcohol and ketone is 91%. The conversion of
cyclododeca-1,5,9-triene to the epoxide (ECDDD) and mono-oxygenated
(CDDA, CDDK) products is 92%.
Example 3
[0042] In another example, Example 2 is followed identically with
the exception that the reaction is stopped at the end of 3.5 hours,
cooled to <30.degree. C. and vented to ambient pressure. In this
example, the selectivity of the oxidation reaction to epoxy
cyclododeca-6-10-diene and other mono-oxygenated products alcohol
(CDDA) and ketone (CDDK) formation is 95%. The conversion of CDDT
to epoxide (ECDDD) and mono-oxygenated products (CDDA, CDDK) is
81%.
Example 4
[0043] In another example, Example 2 is followed identically with
the following exceptions. The oxidation of cyclododeca-1,5,9-triene
is conducted at temperature controlled to 115+/-3.degree. C. and
the reaction is stopped at the end of 3 hours, cooled to
<30.degree. C. and vented to ambient pressure. The contents were
transferred to glass vessel for the peroxide decomposition and
product isolation. The selectivity of this reaction to epoxy
cyclododeca-6-10-diene and other mono-oxygenated products alcohol
(CDDA) and ketone (CDDK) is 93%. The conversion of CDDT to epoxide
(ECDDD) and mono-oxygenated products (CDDA, CDDK) is 84%.
Example 5
[0044] In another example, cyclododeca-1,5,9-triene (40.5 grams,
0.25 mole) is charged to an autoclave reactor along with an
initiator (0.35% w/w). The autoclave is sealed and the air is
displaced by nitrogen gas. Agitation is started and the autoclave
is heated to 100.degree. C. After the reactor temperature attains
100.degree. C., the nitrogen gas is flushed out with nitrogen and
oxygen gas mixture (1:1 by weight %) and pressurized to 100 psig,
ca. 790 kPa. The reaction is run in a semi-continuous mode. The
pressure in the reactor is maintained continuously with the aid of
a control valve set at 100 psig and a reactor outlet vent valve is
set to relieve an amount of gas equivalent to the amount of gas
added to the reactor. The reaction temperature is controlled at
100.+-.3.degree. C. with the aid of a cooling loop inside the
reactor. Samples taken intermittently are quantitatively analyzed
by the analytical methods above to monitor the progress of the
reaction. The reaction is stopped at the end of 3 hours, cooled to
<30.degree. C. and vented to ambient pressure. The contents are
transferred to a glass vessel for the peroxide decomposition and
product isolation. The selectivity of this reaction to epoxy
cyclododeca-6-10-diene and other mono-oxygenated products alcohol
(CDDA) and ketone (CDDK) is 96%. The conversion of CDDT to epoxide
(ECDDD) and mono-oxygenated products (CDDA, CDDK) is 86%.
Example 6
[0045] In an example of an oxidation process, feeding
cyclododeca-1,5,9-triene, heated to 100.degree. C., by means of a
pump to a top portion of a trickle bed reactor column with inert
packing is performed continuously. Oxygen gas preheated at
100.degree. C. is pumped into the trickle bed reactor at two
different levels in the lower half of the column. The pump at the
bottom of the trickle bed reactor circulates liquid from heat
exchanger means. A slip stream sample from the circulation loop,
equivalent to the amount of fresh feed of cyclododeca-1,5,9-triene
is continuously taken out as a reaction product. The pressure in
the reactor is maintained at 100 psig (ca. 790 kPa absolute)
throughout the continuous oxidation reaction by means of a control
valve at a column vent line. The conversion of
cyclododeca-1,5,9-triene into products (ECDDD, CDDA, CDDK) is 94%
and selectivity is 96% at a best selected feed rate.
Example 7
[0046] In yet another example of a continuous oxidation process,
cyclododeca-1,5,9-triene (CDDT) and oxygen gas are preheated
separately to 100.degree. C. and pumped into the bottom of a bubble
column reactor. The pump at the bottom of the bubble column
provides circulation to the liquid after passing through a heat
exchanger. A slip stream sample from the pump circulation loop,
equivalent to the amount of cyclododeca-1,5,9-triene introduced is
continuously taken out as reaction product. The pressure in the
reactor is maintained at 100 psig (ca. 790 kPa absolute) throughout
the continuous oxidation reaction by means of a control valve in a
column vent line. The cyclododeca-1,5,9-triene rate of feed is
varied in order to provide different residence times for the
reaction. The conversion of cyclododeca-1,5,9-triene into products
(ECDDD, CDDA, CDDK) is 96% and selectivity is 97% under a best
selected feed rate for the CDDT.
Example 8
[0047] In yet another example of a continuous oxidation process,
cyclododeca-1,5,9-triene (CDDT) and air are preheated separately to
110.degree. C. and pumped to the top of a trickle bed column
reactor with inert packing. The air preheated to 110.degree. C. is
pumped to the trickle bed reactor at two different levels at the
lower third of the column. The pump at the bottom of the reactor
circulates the liquid passing through a heat exchanger means. A
slip stream sample from the circulation loop equivalent to the
amount of fresh feed of cyclododeca-1,5,9-triene is withdrawn
continuously as reaction product. The pressure in the reactor is
maintained at 120 psig (ca. 930 kPa absolute) for this continuous
reaction by means of a control valve in a vent line of the reactor.
The conversion of cyclododeca-1,5,9-triene into products (ECDDD,
CDDA, CDDK) is 91% and selectivity is 94% under best selected feed
rate for the CDDT.
Example 9
[0048] In yet another example of a continuous oxidation process,
CDDT (cyclododeca-1,5,9-triene) and air preheated separately to
110.degree. C. are pumped into the bottom of a bubble column
reactor. The pump at the bottom of the bubble column circulates the
liquid passing through heat exchanger means. A slip stream sample
taken from the circulation loop equivalent to the amount of fresh
feed of CDDT is continuously withdrawn as reaction product. The
pressure in the reactor is maintained at 110 psig (ca. 860 kPa
absolute) throughout this continuous reaction by means of a control
valve in the reactor vent line. The CDDT feed rate is varied in
order to provide different residence times for the reaction. The
conversion of cyclododeca-1,5,9-triene into products (ECDDD, CDDA,
CDDK) is 93% and selectivity is 96% under a selected best feed rate
for CDDT.
Example 10
[0049] The reaction products from Examples 1 to 8 are collected and
individually distilled in a glass apparatus under reduced pressure.
The small fraction collected at 130.degree. C. comprises
predominately the unreacted cyclododeca-1,5,9-triene. The main
fraction collected from 145-155.degree. C. will comprise
predominately epoxycyclododeca-5,9-diene and minor amounts of
cyclododeca-2,6,10-trienol and cyclododeca-2,6,10-trienone.
Example 11
[0050] In an example, 40 grams of product collected from a process
according to Example 8 are subjected to a distillation process
according to Example 10. A fraction collected between
145-155.degree. C. is transferred to a high pressure autoclave. A
hydrogen reduction catalyst comprising palladium on carbon is
introduced. The autoclave is sealed, the air is displaced
completely with hydrogen gas and the autoclave is heated to
220.degree. C. Additional hydrogen gas is provided and the pressure
is maintained at 1300 psig (ca. 9000 kPa absolute) for 12 hours.
The autoclave is cooled to 100.degree. C., a sample is taken for
analysis and transferred into a glass reactor prior to
solidification. The sample taken is identified as cyclododecanol
(CDDA) having a purity of 98.5%, the yield is 97%.
Example 12
[0051] In an example, cyclododecanol (CDDA) is dehydrogenated
continuously with the aid of a fixed bed catalyst. A catalyst
comprising Raney-Nickel or a substantial equivalent catalyst will
effect dehydrogenation of CDDA to cyclododecanone (CDDK). The
dehydrogenation temperature range is selected to be between
120.degree. C. and 350.degree. C. The yield of CDDK is 98% at the
best selecting dehydrogenation conditions.
Example 13
[0052] In an example, cyclododecanone (CDDK) (36.8 g, 0.20 moles)
is heated with an excess of nitric acid and a V/Cu catalyst (e.g.,
ammonium vanadate and copper nitrate) in a glass reactor for 1
hour. A portion of the reaction work-up is evaporated and then
allowed to cool. A product of the reaction is identified as
dodecanedioic acid (DDDA) after crystallization from solution. The
crystallized DDDA is further filtered and washed with cold water. A
purity for the DDDA is expected to be 99% and the yield based on
cyclododecanol is 88%. The filtrate upon further evaporation and
crystallization will provide another crop of crystals comprising
mixed dicarboxylic acids of 12, 11, 10, 9, 8 and 7 carbon atoms.
The combined overall yields of DDDA and mixed di-acids based on
CDDK are about 94%.
Example 14
[0053] In an example, cyclododecanone (CDDK) (36.8 g, 0.20 moles)
is dissolved in an equal weight of acetic anhydride (in an
embodiment, maleic anhydride may be an equally effective acid
anhydride) and is added to a reactor containing hydrogen peroxide
(50%, 81.6 g, 1.2 moles), acetic anhydride (280 g). The reactor is
provided with an acid catalyst selected on the basis of its
pK.sub.a (such as: pK.sub.a 0 to 5 or using an acid like
dichloroacetic acid) in order to promote the Baeyer-Villiger
oxidation of cyclododecanone and substantial conversion to
laurolactone. This conversion of CDDK to laurolactone is expected
to be greater than 99% with selectivity greater than 95% under the
reaction conditions herein provided.
[0054] Baeyer-Villiger oxidation model reaction:
R--(C.dbd.O)--R+H--O--O--H+cat(dichloroacetic
acid)=R--(C.dbd.O)--O--R
In this case, the R groups of R--(C.dbd.O)--R are in a cyclic
arrangement and the product, R--(C.dbd.O)--O--R, is likewise cyclic
and thus a "lactone" or cyclic ester.
[0055] It should be noted that ratios, concentrations, amounts, and
other numerical data may be expressed herein in a range format. It
is to be understood that such a range format is used for
convenience and brevity, and thus, should be interpreted in a
flexible manner to include not only the numerical values explicitly
recited as the limits of the range, but also to include all the
individual numerical values or sub-ranges encompassed within that
range as if each numerical value and sub-range is explicitly
recited. To illustrate, a concentration range of "about 0.1% to
about 5%" should be interpreted to include not only the explicitly
recited concentration of about 0.1 wt % to about 5 wt %, but also
include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and
the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and 4.4%) within the
indicated range. The term "about" can include .+-.1%, .+-.2%,
.+-.3%, .+-.4%, .+-.5%, .+-.6%, .+-.7%, .+-.8%, .+-.9%, or .+-.10%,
or more of the numerical value(s) being modified. The value of
"about" will not be outside of a reasonable amount considering the
teachings of the present disclosure. In addition, the phrase "about
`x` to `y`" includes "about `x` to about `y`".
[0056] Many variations and modifications may be made to the
above-described embodiments. All such modifications and variations
are intended to be included herein within the scope of this
disclosure and protected by the following claims.
* * * * *